Effect of pore structure on shale oil accumulation in the lower third member of the Shahejie formation,Zhanhua Sag,eastern China: Evidence from gas adsorption and nuclear magnetic resonance

As shale oil occurs primarily in micro–nano pores and fractures, research about the effect of pore structure on shale oil accumulation has great significance for shale oil exploration and development. The effect of pore structure on shale oil accumulation in the lower third member of the Shahejie formation (Es₃^l), Zhanhua Sag, eastern China was investigated using gas adsorption, soxhlet extraction, nuclear magnetic resonance (NMR) analysis, and field emission scanning electron microscope (FE-SEM) observation. The results indicated that the samples contained a larger amount of ink-bottle-shaped and slit-shaped pores after extraction than before extraction. The pore volume and specific surface area of the samples were approximately 2.5 times larger after extraction than before extraction. Residual hydrocarbon occurred primarily in the free-state form in pores with diameters of 10–1000 nm, which can provide sufficient pore volume for free hydrocarbon accumulation. Therefore, pores with diameters of 10–1000 nm were regarded as “oil-enriched pores”, which are effective pores for shale oil exploration, whereas pores with diameters smaller than 10 nm were regarded as “oil-ineffective pores”. Samples with only well-developed small pores with diameters smaller than 1000 nm showed high oil saturation, whereas samples with both small pores and also relatively large pores and micro-fractures presented low oil saturation. As the minimum pore size allowing fluid expulsion is 1000 nm, pores with diameters greater than 1000 nm were considered as “oil-percolated pores”. Large pores and micro-fractures are generally interconnected and may even form a complex fracture mesh, which greatly improves the permeability of shale reservoirs and is beneficial to fluid discharge.     

沾化凹陷页岩油储层特征及控制因素

为确定沾化凹陷古近系沙河街组三段下亚段(沙三下亚段)页岩油储层特征及控制因素,开展了岩心、薄片、扫描电镜、X-射线衍射、物性、有机碳含量、岩石热解等分析测试工作。根据岩石矿物成分和显微沉积构造,可将研究区湖相泥页岩分为7类岩石类型。储集空间包括裂缝和孔隙2种类型,其中,裂缝主要有4类,即构造裂缝、异常压力缝、矿物收缩裂缝和层间微裂缝,前二者在岩心上清晰可见,后二者宽度为微米级别;孔隙主要有3类,即重结晶晶间孔、有机质演化孔和溶蚀孔隙,为纳米到微米级别。研究区页岩油储层发育的控制因素主要有4项：岩石矿物成分和显微沉积构造、有机质含量及赋存方式、成岩作用以及构造作用,在对各控制因素详细分析的基础上,选取方解石含量、纹层状构造、TOC、Ro、孔隙度及综合破裂率6项参数做为页岩油储层评价的关键参数,将沾化凹陷页岩油储层分为优质储层、有利储层和不利储层3类。     

Heterogeneous nanoporosity of the Silurian Longmaxi Formation shale gas reservoir in the Sichuan Basin using the QEMSCAN,FIB-SEM,and nano-CT methods

Nanoporosity of a shale gas reservoir provides essential information on the gas accumulation space and controls the gas reserves. The characteristics of heterogeneous nanoporosity of four shale samples are analyzed by combining quantitative evaluation of minerals by scanning electronic microscopy (QEMSCAN), focused ion beam-scanning electron microscopy (FIB-SEM), and nano-CT. The representative elementary area (REA) is proposed by QEMSCAN to detect the imaging area that can represent the overall contents of minerals and organic matter. Combined with the statistics of pores in minerals and organic matter by FIB-SEM, the quantitative nanoporosity is obtained. The nano-CT is used to compare the total nanoporosity that was obtained by FIB-SEM. The results show that shale has distinct characteristics in nanoporosities due to the variation in organic matter and mineral content. The major pore sizes of the organic matter and clay minerals are smaller than 400 nanometers (nm), and the pore sizes of feldspar and pyrite are mainly 200–600 nm. The pore sizes for pores developed in quartz and carbonate minerals range from a few nanometers to 1000 nm. Furthermore, pores smaller than 400 nm mainly provide the total nanoporosity. The nanoporosities in the organic matter are approximately 17%–21%. Since the organic matter content (0.54%–6.98%) is low, the organic matter contributes approximately 5%–33% of the total nanoporosity in shale. Conversely, the nanoporosities in quartz and clay are generally lower than 3%. Since the mineral content (93.02%–99.46%) is obviously higher than the organic matter content, the minerals contribute approximately 67%–95% of the total nanoporosity in shale.     

Pore characteristic analysis of a lacustrine shale: A case study in the Ordos Basin,NW China

Organic shales deposited in a continental environment are well developed in the Ordos Basin, NW China, which is rich in hydrocarbons. However, previous research concerning shales has predominantly focused on marine shales and barely on continental shales. In this study, geochemical and mineralogical analyses, high-pressure mercury intrusion and low-pressure adsorption were performed on 18 continental shale samples obtained from a currently active shale gas play, the Chang 7 member of Yanchang Formation in the Ordos Basin. A comparison of all these techniques is provided for characterizing the complex pore structure of continental shales.Geochemical analysis reveals total organic carbon (TOC) values ranging from 0.47% to 11.44%, indicating that there is abundant organic matter (OM) in the study area. Kerogen analysis shows vitrinite reflectance (Ro) of 0.68%–1.02%, indicating that kerogen is at a mature oil generation stage. X-ray diffraction mineralogy (XRD) analysis indicates that the dominant mineral constituents of shale samples are clay minerals (which mainly consist of illite, chlorite, kaolinite, and negligible amounts of montmorillonite), quartz and feldspar, followed by low carbonate content. All-scale pore size analysis indicates that the pore size distribution (PSD) of shale pores is mainly from 0.3 to 60 nm. Note that accuracy of all-scale PSD analysis decreases for pores less than 0.3 nm and more than 10 μm. Experimental analysis indicates that mesopores (2–50 nm) are dominant in continental shales, followed by micropores (<2 nm) and macropores (50 nm–10 μm). Mesopores have the largest contribution to pore volume (PV) and specific surface area (SSA). In addition, plate- and sheet-shaped pores are dominant with poor connectivity, followed by hybrid pores. Results of research on factors controlling pore structure development show that it is principally controlled by clay mineral contents and Ro, and this is different from marine systems. This study has important significance in gaining a comprehensive understanding of continental shale pore structure and the shale gas storage–seepage mechanism.     

Diagenesis and origin of calcite cement in the Flemish Pass Basin sandstone reservoir (Upper Jurassic): Implications for porosity development

The Flemish Pass Basin is a deep-water basin located offshore on the continental passive margin of the Grand Banks, eastern Newfoundland, which is currently a hydrocarbon exploration target. The current study investigates the petrographic characteristics and origin of carbonate cements in the Ti-3 Member, a primary clastic reservoir interval of the Bodhrán Formation (Upper Jurassic) in the Flemish Pass Basin.The Ti-3 sandstones with average Q_86.0F_3.1R_10.9 contain various diagenetic minerals, including calcite, pyrite, quartz overgrowth, dolomite and siderite. Based on the volume of calcite cement, the investigated sandstones can be classified into (1) calcite-cemented intervals (>20% calcite), and (2) poorly calcite-cemented intervals (porous). Petrographic analysis shows that the dominant cement is intergranular poikilotopic (300–500 μm) calcite, which stared to form extensively at early diagenesis. The precipitation of calcite occured after feldspar leaching and was followed by corrosion of quartz grains. Intergranular calcite cement hosts all-liquid inclusions mainly in the crystal core, but rare primary two-phase (liquid and vapor) fluid inclusions in the rims ((with mean homogenization temperature (T_h) of 70.2 ± 4.9 °C and salinity estimates of 8.8 ± 1.2 eq. wt.% NaCl). The mean δ¹⁸O and δ¹³C isotopic compositions of the intergranular calcite are −8.3 ± 1.2‰, VPDB and −3.0 ± 1.3‰, VPDB, respectively; whereas, fracture-filling calcite has more depleted δ¹⁸O but similar δ¹³C values. The shale normalized rare earth element (REE_SN) patterns of calcite are generally parallel and exhibit slightly negative Ce anomalies and positive Eu anomalies. Fluid-inclusion gas ratios (CO₂/CH₄ and N₂/Ar) of calcite cement further confirms that diagenetic fluids originated from modified seawater. Combined evidence from petrographic, microthermometric and geochemical analyses suggest that (1) the intergranular calcite cement precipitated from diagenetic fluids of mixed marine and meteoric (riverine) waters in suboxic conditions; (2)the cement was sourced from the oxidation of organic matters and the dissolution of biogenic marine carbonates within sandstone beds or adjacent silty mudstones; and (3) the late phases of the intergranular and fracture-filling calcite cements were deposited from hot circulated basinal fluids.Calcite cementation acts as a main controlling factor on the reservoir quality in the Flemish Pass reservoir sandstones. Over 75% of initial porosity was lost due to the early calcite cementation. The development of secondary porosity (mostly enlarged, moldic pores) and throats by later calcite dissolution due to maturation of organic matters (e.g., hydrocarbon and coals), was the key process in improving the reservoir quality.     

Characterization of shale pore system: A case study of Paleogene Xin'gouzui Formation in the Jianghan basin,China

The pore size classification (micropore <2 nm, mesopore 2–50 nm and macropore >50 nm) of IUPAC (1972) has been commonly used in chemical products and shale gas reservoirs; however, it may be insufficient for shale oil reservoirs. To establish a suitable pore size classification for shale oil reservoirs, the open pore systems of 142 Chinese shales (from Jianghan basin) were studied using mercury intrusion capillary pressure analyses. A quantitative evaluation method for I-micropores (0–25 nm in diameter), II-micropores (25–100 nm), mesopores (100–1000 nm) and macropores (>1000 nm) within shales was established from mercury intrusion curves. This method was verified using fractal geometry theory and argon-ion milling scanning electron microscopy images. Based on the combination of pore size distribution with permeability and average pore radius, six types (I-VI) shale open pore systems were analyzed. Moreover, six types open pore systems were graded as good, medium and poor reservoirs. The controlling factors of pore systems were also investigated according to shale compositions and scanning electron microscopy images. The results show that good reservoirs are composed of shales with type I, II and III pore systems characterized by dominant mesopores (mean 68.12 vol %), a few macropores (mean 7.20 vol %), large porosity (mean 16.83%), an average permeability of 0.823 mD and an average pore radius (r_a) of 88 nm. Type IV pore system shales are medium reservoirs, which have a low oil reservoir potential due to the developed II-micropores (mean 57.67 vol %) and a few of mesopores (mean 20.19 vol %). Poor reservoirs (composed of type V and VI pore systems) are inadequate reservoirs for shale oil due to the high percentage of I-micropores (mean 69.16 vol %), which is unfavorable for the flow of oil in shale. Pore size is controlled by shale compositions (including minerals and organic matter), and arrangement and morphology of mineral particles, resulting in the developments of shale pore systems. High content of siliceous mineral and dolomite with regular morphology are advantage for the development of macro- and mesopores, while high content of clay minerals results in a high content of micropores.     

Novel 3D centimetre-to nano-scale quantification of an organic-rich mudstone: The Carboniferous Bowland Shale,Northern England

X-ray computed tomography and serial block face scanning electron microscopy imaging techniques were used to produce 3D images with a resolution spanning three orders of magnitude from ∼7.7 μm to 7 nm for one typical Bowland Shale sample from Northern England, identified as the largest potential shale gas reservoir in the UK. These images were used to quantitatively assess the size, geometry and connectivity of pores and organic matter. The data revealed four types of porosity: intra-organic pores, organic interface pores, intra- and inter-mineral pores. Pore sizes are bimodal, with peaks at 0.2 μm and 0.04 μm corresponding to pores located at organic–mineral interfaces and within organic matter, respectively. These pore-size distributions were validated by nitrogen adsorption data. The multi-scale imaging of the four pore types shows that there is no connected visible porosity at these scales with equivalent diameter of 20 nm or larger in this sample. However, organic matter and clay minerals are connected and so the meso porosity (<20 nm) within these phases provides possible diffusion transport pathways for gas. This work confirms multi-scale 3D imaging as a powerful quantification method for shale reservoir characterisation allowing the representative volumes of pores, organic and mineral phases to be defined to model shale systems. The absence of connected porosity at scales greater than 20 nm indicates the likely importance of the organic matter network, and associated smaller-scale pores, in controlling hydrocarbon transport. . The application of these techniques to shale gas plays more widely should lead to a greater understanding of properties in the low permeability systems.     

Mineral types and organic matters of the Ordovician-Silurian Wufeng and Longmaxi Shale in the Sichuan Basin,China: Implications for pore systems,diagenetic pathways,and reservoir quality in fine-grained sedimentary rocks

Mineral types (detrital and authigenic) and organic-matter components of the Ordovician-Silurian Wufeng and Longmaxi Shale (siliceous, silty, argillaceous, and calcareous/dolomitic shales) in the Sichuan Basin, China are used as a case study to understand the control of grain assemblages and organic matter on pores systems, diagenetic pathway, and reservoir quality in fine-grained sedimentary rocks. This study has been achieved using a combination of petrographic, geochemical, and mercury intrusion methods. The results reveal that siliceous shale comprises an abundant amount of diagenetic quartz (40–60% by volume), and authigenic microcrystalline quartz aggregates inhibit compaction and preserve internal primary pores as rigid framework for oil filling during oil window. Although silty shale contains a large number of detrital silt-size grains (30–50% by volume), which is beneficial to preserve interparticle pores, the volumetric contribution of interparticle pores (mainly macropores) is small. Argillaceous shale with abundant extrabasinal clay minerals (>50% by volume) undergoes mechanical and chemical compactions during burial, leading to a near-absence of primary interparticle pores, while pores preserved between clay platelets are dominant with more than 10 nm in pore size. Pore-filling calcite and dolomite precipitated during early diagenesis inhibit later compaction in calcareous/dolomitic shale, but the cementation significantly reduces the primary interparticle pores. Pore-throat size distributions of dolomitic shale show a similar trend with silty shale. Besides argillaceous shale, all of the other lithofacies are dominated by OM pores, which contribute more micropores and mesopores and is positively related to TOC and quartz contents. The relationship between pore-throat size and pore volume shows that most pore volumes are provided by pore throats with diameters <50 nm, with a proportion in the order of siliceous (80.3%) > calcareous/dolomitic (78.4%) > silty (74.9%) > argillaceous (61.3%) shales. In addition, development degree and pore size of OM pores in different diagenetic pathway with the same OM type and maturity show an obvious difference. Therefore, we suggest that the development of OM pores should take OM occurrence into account, which is related to physical interaction between OM and inorganic minerals during burial diagenesis. Migrated OM in siliceous shale with its large connected networks is beneficial for forming more and larger pores during gas window. The result of the present work implies that the study of mineral types (detrital and authigenic) and organic matter-pores are better understanding the reservoir quality in fine-grained sedimentary rocks.     

Qualitative and quantitative characterization of a transitional shale reservoir: A case study from the Upper Carboniferous Taiyuan shale in the eastern uplift of Liaohe Depression,China

The paper takes the Upper Carboniferous Taiyuan shale in eastern uplift of Liaohe depression as an example to qualitatively and quantitatively characterize the transitional (coal-associated coastal swamp) shale reservoir. Focused Ion Beam Scanning Electron Microscope (FIB-SEM), nano-CT, helium pycnometry, high-pressure mercury intrusion and low-pressure gas (N₂ & CO₂) adsorption for eight shale samples were taken to investigate the pore structures. Four types of pores, i.e., organic matter (OM) pores, interparticle (InterP) pores, intraparticle (IntraP) pores and micro-fractures are identified in the shale reservoir. Among them, intraP pores and micro-fractures are the major pore types. Slit-shaped pores are the major shape in the pore system, and the connectivity of the pore-throat system is interpreted to be moderate, which is subordinate to marine shale. The porosity from three dimension (3D) reconstruction of SEM images is lower than the porosity of helium pycnometry, while the porosity trend of the above two methods is the same. Combination of mercury intrusion and gas absorption reveals that nanometer-scale pores provide the main storage space, accounting for 87.16% of the pore volume and 99.85% of the surface area. Micropores contribute 34.74% of the total pore volume and 74.92% of the total pore surface area; and mesopores account for 48.27% of the total pore volume and 24.93% of the total pore surface area; and macropores contribute 16.99% of the total pore volume and 0.15% of the total pore surface area. Pores with a diameter of less than 10 nm contribute the most to the pore volume and the surface area, accounting for 70.29% and 97.70%, respectively. Based on single factor analysis, clay minerals are positively related to the volume and surface area of micropores, mesopores and macropores, which finally control the free gas in pores and adsorbed gas content on surface area. Unlike marine shale, TOC contributes little to the development of micropores. Brittle minerals inhibit pore development of Taiyuan shale, which proves the influence of clay minerals in the pore system.     

Organic geochemistry and reservoir characterization of the organic matter-rich calcilutite in the Shulu Sag,Bohai Bay Basin,North China

Although extensive studies have been conducted on unconventional mudstone (shales) reservoirs in recent years, little work has been performed on unconventional tight organic matter-rich, fine-grained carbonate reservoirs. The Shulu Sag is located in the southwestern corner of the Jizhong Depression in the Bohai Bay Basin and filled with 400–1000 m of Eocene lacustrine organic matter-rich carbonates. The study of the organic matter-rich calcilutite in the Shulu Sag will provide a good opportunity to improve our knowledge of unconventional tight oil in North China. The dominant minerals of calcilutite rocks in the Shulu Sag are carbonates (including calcite and dolomite), with an average of 61.5 wt.%. The carbonate particles are predominantly in the clay to silt size range. Three lithofacies were identified: laminated calcilutite, massive calcilutite, and calcisiltite–calcilutite. The calcilutite rocks (including all the three lithofacies) in the third unit of the Shahejie Formation in the Eocene (Es₃) have total organic carbon (TOC) values ranging from 0.12 to 7.97 wt.%, with an average of 1.66 wt.%. Most of the analyzed samples have good, very good or excellent hydrocarbon potential. The organic matter in the Shulu samples is predominantly of Type I to Type II kerogen, with minor amounts of Type III kerogen. The temperature of maximum yield of pyrolysate (T_max) values range from 424 to 452 °C (with an average of 444 °C) indicating most of samples are thermally mature with respect to oil generation. The calcilutite samples have the free hydrocarbons (S₁) values from 0.03 to 2.32 mg HC/g rock, with an average of 0.5 mg HC/g rock, the hydrocarbons cracked from kerogen (S₂) yield values in the range of 0.08–57.08 mg HC/g rock, with an average of 9.06 mg HC/g rock, and hydrogen index (HI) values in the range of 55–749 mg HC/g TOC, with an average of 464 mg HC/g TOC. The organic-rich calcilutite of the Shulu Sag has very good source rock generative potential and have obtained thermal maturity levels equivalent to the oil window. The pores in the Shulu calcilutite are of various types and sizes and were divided into three types: (1) pores within organic matter, (2) interparticle pores between detrital or authigenic particles, and (3) intraparticle pores within detrital grains or crystals. Fractures in the Shulu calcilutite are parallel to bedding, high angle, and vertical, having a significant effect on hydrocarbon migration and production. The organic matter and dolomite contents are the main factors that control calcilutite reservoir quality in the Shulu Sag.     

BIB-SEM characterization of pore space morphology and distribution in postmature to overmature samples from the Haynesville and Bossier Shales

Four Haynesville Shale and four Bossier Shale samples were investigated using a combination of Scanning Electron Microscopy (SEM) and Broad Ion Beam (BIB) polishing. This approach enables the microstructure and porosity to be studied down to the mesopore size (<50 nm) in representative areas at the scale of the BIB cross-sections. The samples vary in mineralogy, grain size and TOC and the maturity ranges from 2.42 to 2.58 VR_r in the Haynesville Shale to 1.79–2.26 VR_r in the Bossier Shale. This variety within the samples enabled us to study controls on the porosity distribution in these shales. Visible pores exist as intraparticle pores mainly in carbonate grains and pyrite framboids and as interparticle pores, mainly in the clay-rich matrix. Pores in organic matter show a characteristic porosity with respect to the type of organic matter, which mainly consists of mixtures of amorphous organic matter and minerals, organic laminae and discrete macerals. A clear positive trend of organic-matter porosity with maturity was found. Pore sizes are power law distributed in the range of 4.4 μm to at least 36 nm in equivalent diameter. The differences in power law exponents suggest that a more grain supported, coarse-grained matrix may prevent pores from mechanical compaction. Porosities measured in the BIB cross-sections were significantly lower in comparison to porosities obtained by Mercury Intrusion Porosimetry (MIP). This difference is mainly attributed to the different resolution achieved with BIB-SEM and MIP and type of pore network. Extrapolation of pore size distributions (PSDs) enables the BIB-SEM porosity to be estimated down to the resolution of the MIP and thus to upscale microstructural observation at the confined space of the BIB-SEM method to bulk porosity measurement. These inferred porosities are in good agreement with the MIP determined porosities, which underpins the assumption that pores segmented in BIB-SEM mosaics are representative of the MIP methodology.     

Pore structure of Cambrian shales from the Sichuan Basin in China and implications to gas storage

The microstructure of black siliceous shale from the lower Cambrian Niutitang Formation, Sichuan Basin in China was investigated by the combination of field emission scanning electron microscope (FE-SEM) and argon ion beam milling. The nanometer-to micrometer-scale pore systems of shales are an important control on gas storage and fluid migration. In this paper, the organic porosity in shale samples within oil and gas window has been investigated, and the formation mechanism and diagenetic evolution of nanopores have been researched.FE-SEM reveals five pore types that are classified as follows: organic nanopores, pores in clay minerals, nanopores of framework minerals, intragranular pores in microfossils, and microfractures. Numerous organic nanopores are observed in shales in the gas window, whereas microfractures can be seen within the organic matter of shales in the oil window. Microfractures in oil window shales could be attributed to pressure buildup in the organic matter when incompressible liquid hydrocarbon are generated, and the orientation of microfractures is probably parallel to the bedding and strength anisotropy of the formation. Pores in clay minerals are always associated with the framework of clay flakes, and develop around rigid mineral grains because the pressure shadows of mineral grains protect pores from collapse, and the increasing of silt content would lead to an increase in pressure shadows and improve porosity. Nanopores of rock framework are probably related to dissolution by acidic fluids from hydrocarbon generation, and the dissolution-related pores promote permeability of shales. Porosity in the low-TOC, low-thermal-maturity shales contrast greatly with those of high-TOC, high-thermal-maturity shales. While the high-TOC shales contain abundant organic microporosity, the inorganic pores can contribute a lot to the porosity of the low-TOC shales.     

2D and 3D nanopore characterization of gas shale in Longmaxi formation based on FIB-SEM

Studying complex pore structures is the key to understanding the mechanism of shale gas accumulation. FIB-SEM (focused ion beam-scanning electron microscope) is the mainstream and effective instrument for imaging nanopores in gas shales. Based on this technology, 2D and 3D characteristics of shale samples from Lower Silurian Longmaxi formation in southern Sichuan Basin were investigated. 2D experimental results show that the pores in shale are nanometer-sized, and the structure of those nanopores can be classified into three types: organic pores, inorganic pores and micro fractures. Among the three types, organic pores are dominantly developed in the OM (organic matter) with three patterns such as continuous distributed OM, OM between clay minerals and OM between pyrite particles, and the size of organic pores range from 5 nm to 200 nm.Inveresly, inorganic pores and micro fractures are less developed in the Longmaxi shales. 3D digital rocks were reconstructed and segmented by 600 continuous images by FIB cutting and SEM imaging simultaneously. The pore size distribution and porosity can be calculated by this 3D digital core, showing that its average value is 32 nm and porosity is 3.62%.The 3D digital porosity is higher than its helium porosity, which can be regarded as one important parameter for evaluation of shale gas reserves. The 2D and 3D characterized results suggest that the nanometer-sized pores in organic matter take up the fundamental storage space for the Longmaxi shale. These characteristics have contributed to the preservation of shale gas in this complex tectonic area.     

Nano-scale pore structure and fractal dimension of organic-rich Wufeng-Longmaxi shale from Jiaoshiba area,Sichuan Basin: Investigations using FE-SEM,gas adsorption and helium pycnometry

Much attention have been recently paid to the upper Ordovician Wufeng shale (O₃w) and lower Silurian Longmaxi shale (S₁l) in the Jiaoshiba area of Sichuan Basin, which is now the largest producing shale gas field in China. Field emission scanning electron microscopy (FE-SEM), low pressure gas (N₂ and CO₂) adsorption, helium pycnometry, X-ray diffraction and geochemical analyses were performed to investigate the pore structure and fractal dimension of the pores in O₃w-S₁l shale formation in the Jiaoshiba area. FE-SEM images show that organic matter (OM) pores are dominant in the organic-rich samples and these pores are often irregular, bubble-like, elliptical and faveolate in shape, while in organic-poor samples, limited and isolated interparticle (interP), intraparticle (intraP) and OM pores are observed. Reversed S-shaped isotherms obtained from nitrogen adsorption are type Ⅱ, and hysteresis loops indicate that the shape of micropore in the samples is slit-or plate-like. BET surface areas and total pore volume vary from 12.2 to 27.1 m²/g and from 1.8 × 10⁻² to 2.9 × 10⁻² cm³/g, with an average of 19.5 m²/g and 2.3 × 10⁻² cm³/g, respectively. Adsorption volume from both N₂ and CO₂ adsorption increases with respect to TOC contents. Porosities obtained from helium porosimetry are comparable with these from gas (CO₂ and N₂) adsorption in O₃w-S₁l shale. However, porosity determined by quantitative FE-SEM analysis is much smaller, which is mainly related to limited resolution and the small areas of investigation.Based on the Frenkel-Halsey-Hill (FHH) model of low-pressure N₂ adsorption, fractal dimensions of the pores varied from 2.737 to 2.823. Relationships between pore structure parameters and TOC content, mineral composition and fractal dimension reveal that the fractal dimension is mainly associated with micropores. Samples with higher TOC content, higher quartz content and lower clay content tend to contain more heterogeneous micropores, resulting in higher fractal dimensions and more complicated pore structure in shales. Therefore, fractal dimension is an effective parameter to reflect the complexity of pore structure and the degree of micropore development in O₃w-S₁l shale.     

Pore characterization and methane sorption capacity of over-mature organic-rich Wufeng and Longmaxi shales in the southeast Sichuan Basin,China

Currently, the Upper Ordovician Wufeng (O₃w) and Lower Silurian Longmaxi (S₁l) Formations in southeast Sichuan Basin have been regarded as one of the most important target plays of shale gas in China. In this work, using a combination of low-pressure gas adsorption (N₂ and CO₂), mercury injection porosimetry (MIP) and high-pressure CH₄ adsorption, we investigate the pore characteristics and methane sorption capacity of the over-mature shales, and discuss the main controlling factors for methane sorption capacity and distribution of methane gas in pore spaces.Low pressure CO₂ gas adsorption shows that micropore volumes are characterized by three volumetric maxima (at about 0.35, 0.5 and 0.85 nm). The reversed S-shaped N₂ adsorption isotherms are type Ⅱ with hysteresis being noticeable in all the samples. The shapes of hysteresis loop are similar to the H3 type, indicating the pores are slit- or plate-like. Mesopore size distributions are unimodal and pores with diameters of 2–16 nm account for the majority of mesopore volume, which is generally consistent with MIP results. The methane sorption capacities of O₃w-S₁l shales are in a range of 1.63–3.66 m³/t at 30 °C and 10 MPa. Methane sorption capacity increase with the TOC content, surface area and micropore volume, suggesting organic matter might provide abundant adsorption site and enhance the strong methane sorption capacity. Samples with higher quartz content and lower clay content have larger sorption capacity. Our data confirmed that the effects of temperature and pressure on methane sorption capacity of shale formation are opposite to some extent, suggesting that, during the burial or uplift stage, the gas sorption capacity of hydrocarbon reservoirs can be expressed as a function of burial depth. Based on the adsorption energy theory, when the pore diameter is larger than 2 nm, much methane molecular will be adsorbed in pores space with distance to pore wall less than 2 nm; while free gas is mainly stored in the pore space with distance to pore wall larger than 2 nm. Distributions of adsorption space decrease with the increasing pore size, while free gas volume increase gradually, assuming the pore are cylindrical or sphere. Particularly, when the pore size is larger than 30 nm, the content of adsorbed gas space volume is very low and its contribution to the all gas content is negligible.     

Relationships between porosity,organic matter,and mineral matter in mature organic-rich marine mudstones of the Belle Fourche and Second White Specks formations in Alberta,Canada

This study presents approaches for evaluating hybrid source rock/reservoirs within tight-rock petroleum systems. The emerging hybrid source rock/reservoir shale play in the Upper Cretaceous Second White Specks and Belle Fourche formations in central Alberta, Canada is used as an example to evaluate organic and inorganic compositions and their relationships to pore characteristics. Nineteen samples from a 77.5 m-long core were analyzed using organic petrography, organic geochemistry, several methods of pore characterization, and X-ray powder diffraction (XRD). The lower part of the studied section includes quartz- and clay-rich mudrocks of the Belle Fourche Formation with low carbonate content, whereas the upper portion contains calcareous mudrocks of the Second White Specks Formation. Strata are mineralogically composed of quartz plus albite (18–56 wt. %), carbonates (calcite, dolomite, ankerite; 1–65 wt. %), clays (illite, kaolinite, chlorite; 15–46 wt. %), and pyrite (2–12 wt. %). Petrographic examinations document that organic matter represents marine Type II kerogen partly biodegraded with limited terrestrial input. Vitrinite reflectance R_o (0.74–0.87%), T_max values (438–446 °C) and biomarkers indicate mid-maturity within the oil window. The relatively poor remaining hydrocarbon potential, expressed as an S2 value between 2.1 and 6.5 mg HC/g rock, may result from an estimated 60–83% of the original kerogen having been converted to hydrocarbons, with the bulk having migrated to adjacent sandstone reservoirs. However, the present-day remaining total organic carbon TOC_pd content remains relatively high (1.7–3.6 wt. %), compared with the estimated original TOC_o of 2.4–5.0 wt. %. The calculated transformation ratio of 60–83% suggests that the remaining 17–40 wt. % of kerogen is able to generate more hydrocarbons. The studied section is a tight reservoir with an average Swanson permeability of 3.37·10⁻⁵ mD (measured on two samples) and total porosity between 1.7 and 5.0 vol. % (3 vol. % on average). The upper part of the sandy Belle Fourche Formation, with slightly elevated porosity values (3.5–5 vol. %), likely represents the interval with the best reservoir properties in the studied core interval. Total pore volume ranges between 0.0065 and 0.0200 cm³/g (measured by a combination of helium pycnometry and mercury immersion). Mesopores (2–50 nm ∅) are the most abundant pores and occupy 34–67% of total porosity or a volume of 0.0030–0.0081 cm³/g. In comparison, micropores (<2 nm ∅) cover a wide range from 6 to 60% (volume 0.0007–0.0053 cm³/g), and macropores (>50 nm ∅) reach up to 57% with the exception of some samples failing to indicate the presence of this pore fraction (volume 0.0000–0.0107 cm³/g). Macroporosity is mostly responsible for variations in total porosity, as suggested by macroporosity's strongest correlation with total porosity within the section. The relatively narrow ranges of TOC and minerals contents among measured samples limit our ability to further deconvolute factors that influence changes in total porosity and pore size distribution.     

Effects of composition and pore structure on the reservoir gas capacity of Carboniferous shale from Qaidam Basin,China

Shale adsorption and breakthrough pressure are important indicators of shale gas development and key factors in evaluating the reservoir capacities of shales. In this study, geochemical tests, pore-structure tests, methane adsorption tests, and breakthrough-pressure tests were conducted on shales from the Carboniferous Hurleg Formation in eastern Qaidam Basin. The effects of the shale compositions and pore structures on the adsorption and breakthrough pressures were studied, and the reservoir capacities of the shales were evaluated by analyzing the shale adsorptions and sealing effects. The results indicate that the organic carbon content was only one of factors in affecting the adsorption capacity of the shale samples while the effect of the clay minerals was limited. Based on the positive correlation between the adsorption capacity and specific surface area of the shale, the specific surface area of the micropores can be used as an indicator to determine the adsorption capacity of shale. The micro-fracturing of brittle minerals, such as quartz, create a primary path for shale gas breakthrough, whereas the expansion of clay minerals with water greatly increases the breakthrough pressure in the shale samples. Methane adsorption tests showed that maximum methane adsorption for shale samples Z045 and S039 WAS 0.107 and 0.09655 mmol/g, respectively. The breakthrough pressure was 39.36 MPa for sample S039, maintained for 13 days throughout the experiment; however, no breakthrough was observed in sample Z045 when subjected to an injected pressure of 40 MPa for 26 days. This indicates that sample Z045, corresponding to a depth of 846.24 m, exhibited higher adsorption capacity and a better reservoir-sealing effect than sample S039 (498.4 m depth). This study provides useful information for future studies of Qaidam Basin shale gas exploration and development and for evaluation of shale quality.     

苏北盆地阜宁组源储特征及页岩油勘探方向探讨

对苏北盆地重点凹陷的70口钻井采集395件样品进行实验分析,并结合前人资料详细研究了苏北盆地古近系古新统阜宁组阜二段、阜四段两套烃源岩地化特征、岩矿特征、储集空间类型及储集性能,在重点油井解剖的基础上,探讨了页岩油的富集机理。苏北盆地阜宁组有机碳普遍大于 1.0%,有机质类型较好,整体处于低熟-成熟阶段,具备良好的生油基础;微裂缝、孔隙较发育,具有一定的储集条件,阜二段泥页岩整体黏土矿物含量低于35%,脆性矿物含量大于50%,有利于页岩油的开采。通过对重点凹陷典型页岩油藏的两口井的数据解剖,认为页岩油藏受高有机质丰度的成熟泥页岩、脆性矿物含量、裂缝发育程度、异常高压等因素控制。苏北盆地的金湖凹陷、高邮凹陷、海安凹陷和盐城凹陷的深凹带是泥页岩油气勘探和开发的有利区带。     

Diagenesis and reservoir quality of sandstones with ancient “deep” incursion of meteoric freshwater——An example in the Nanpu Sag,Bohai Bay Basin,East China

An example of diagenesis and reservoir quality of buried sandstones with ancient incursion of meteoric freshwater is presented in this study. The interpretation is based on information including porosity and permeability, petrography, stable isotopic composition of authigenic minerals, homogenization temperatures (T_h) of aqueous fluid inclusions (AFIs), and pore water chemistry. These sandstones, closely beneath or far from the regional unconformity formed during the late Paleogene period, are located in the thick Shahejie Formation in the Gaoliu area of Nanpu Sag, Bohai Bay Basin, East China. Early-diagenetic calcite cements were leached to form intergranular secondary pores without precipitation of late-diagenetic calcite cements in most sandstones. Feldspars were leached to form abundant intragranular secondary pores, but with small amounts of concomitant secondary minerals including authigenic quartz and kaolinite. The mass imbalance between the amount of leached minerals and associated secondary minerals suggests that mineral leaching reactions occurred most likely in an open geochemical system, and diagenetic petrography textures suggest that advective flow dominated the transfer of solutes from leached feldspars and calcites. Low salinity and ion concentrations of present pore waters, and extensive water rock interactions suggest significant incursion of meteoric freshwater flux in the sandstones. Distances of the sandstones to the regional unconformity can reach up to 1800 m, while with significant uplift in the Gaoliu area, the burial depth of such sandstones (below sea level) can be less than 800–1000 m during the uplift and initial reburial stage. Significant uplift during the Oligocene period provided substantial hydraulic drive and widely developed faults served as favorable conduits for downward penetration of meteoric freshwater from the earth's surface (unconformity) to these sandstone beds. Extensive feldspar leaching has been occurring since the uplift period. Coupled high T_h (95∼115 °C) of AFI and low δ¹⁸O_(SMOW) values (+17∼+20‰) within the quartz overgrowths show that quartz cementation occurred in the presence of diagenetic modified meteoric freshwater with δ¹⁸O_(SMOW) values of −7∼−2‰, indicating that authigenic quartz only have been formed during the late reburial stage when meteoric fresh water penetration slowed down. Secondary pores in thin sections and tested porosity suggest that meteoric freshwater leaching of feldspars and calcite minerals generated approximately 7–10% enhanced secondary porosity in these sandstones. Meteoric freshwater leaching reactions cannot be ignored in similar sandstones that located deep beneath the unconformity, with great uplift moving these sandstones above or close to sea level and with faults connecting the earth's surface with the sandstone beds.     

Multi-scale pore structure of COx claystone: Towards the prediction of fluid transport

We aim to relate the morphology of the pore network of finely porous claystones to their fluid transport properties. By using Focused Ion Beam in combination with Scanning Electron Microscopy (FIB/SEM), we image the pore network of COx claystone from 2D image stacks and as 3D reconstructed volumes. Our FIB/SEM samples are representative of the mesoscopic matrix clay. Porosity resolvable by this technique is in the range 1.7–5.9% with peak pore sizes of 50–90 nm. 3D pore network skeletonization provides connected pore volumes between end surfaces, tortuosity, density, and shortest pore paths with their pore size distribution. At higher resolution, 2D transmission electron microscopy (TEM) reveals large amounts of smaller pores (2–20 nm) between clay aggregates, associated to a local porosity of 14–25%, and peak sizes of 4–6 nm. Liquid permeability predictions with Katz–Thompson model, at the FIB/SEM volume scale and at the TEM surface scale, are in good agreement with macroscopic measurements (on the order of 10⁻²⁰ m²), showing that both mesopore sizes (peaks at 50–90 nm and 4–6 nm), located within the clay matrix, contribute to liquid transport.